• Title/Summary/Keyword: Coordination chemistry

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Synthesis, Structure, and Magnetic Properties of 1D Nickel Coordination Polymer Ni(en)(ox)·2H2O (en = ethylenediamine; ox = oxalate)

  • Chun, Ji-Eun;Lee, Yu-Mi;Pyo, Seung-Moon;Im, Chan;Kim, Seung-Joo;Yun, Ho-Seop;Do, Jung-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.30 no.7
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    • pp.1603-1606
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    • 2009
  • A new 1D oxalato bridged compound Ni(en)(ox)-2$H_2$O, (ox = oxalate; en = ethylenediamine) has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, IR spectrum, TG analysis, and magnetic measurements. In the structure the Ni atoms are coordinated with four oxygen atoms in two oxalate ions and two nitrogen atoms in one ethylenediamine molecule. The oxalate anion acts as a bis-bidentate ligand bridging Ni atoms in cis-configuration. This completes the infinite zigzag neutral chain, [Ni(en)(ox)]. The interchain space is filled by water molecules that link the chains through a network of hydrogen bonds. Thermal variance of the magnetic susceptibility shows a broad maximum around 50 K characteristic of one-dimensional antiferromagnetic coupling. The theoretical fit of the data for T > 20 K led to the nearest neighbor spin interaction J = -43 K and g = 2.25. The rapid decrease in susceptibility below 20 K indicate this compound to be a likely Haldane gap candidate material with S = 1.

Structure of a Copper(Ⅱ) Hexaazamacrotricyclic Complex : (1,3,6,9,11,14-Hexaazatricyclo[12.2.1.16,9]octadecane)-copper(Ⅱ) Perchlorate

  • Cheon Manseog;Suh Paik Myunghyun;Shin Whanchul
    • Bulletin of the Korean Chemical Society
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    • v.13 no.4
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    • pp.363-367
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    • 1992
  • The crystal structure of (1,3,6,9,11,14-hexaazatricycol[12.2.1.$1^{6,9}$]octadecane)copper(Ⅱ) perchlorate, Cu($C_{12}H_{26}N_6$)$(ClO_4)_2$, has been determined by the X-ray diffraction methods. The crystal data are as follows: Mr=516.9, triclinic, ${\alpha}=8.572\;(2)$, b=8.499 (3), c=15.204 (3) ${\AA}$, ${\alpha}=80.42\;(5),\;{\beta}=73.57\;(3),\;{\gamma}=69.82\;(4)^{\circ},\;V=994.2\;{\AA}^3,\;D_C=1.726\;gcm^{-3}$, space group $P{\tilde{1}},\;Z=2,\;{\mu}=21.27\;cm^{-1}&, F(000)=534 and T=297 K. The structure was solved by direct methods and refined by full-matrix least-squares methods to and R value of 0.081 for 1608 observed reflections measured with graphite-mono-chromated Mo Ka radiation on a diffractometer. There are two independent complexes in the unit cell. The two copper ions lie at the special positions (1/2, 0, 0) and (0, 1/2, 1/2)and each complex possesses crystallographic center of symmetry. Each Cu ion is coordinated to four nitrogen donors if the hexaazamacrotricyclic ligand and weakly interacts with two oxygen atoms of the perchlorate ions to form a tetragonally distorted octahedral coordination geometry. The Cu_N (sec), Cu_N(tert) and Cu_O coordination distances are 1.985 (14), 2.055 (14) and 2.757 (13) ${\AA}$ for the complex A and 1.996 (10), 2.040 (11) and 2.660 (13) ${\AA}$ for the complex B, respectively. The macrocycles in the two independent cations assume a similar conformation with the average r.m.s. deviation of 0.073 ${\AA}$. Two 1,3-diazacyclopentane ring moieties of the hexaazamacrotricyclic ligand are placed oppositely and almost perpendicularly to the square coordination plane of the ruffled 14-membered macrocycle. The secondary N atoms are hydrogen-bonded to the perchlorate O atoms with distances of 3.017 (23) and 3.025 (19) ${\AA}$ for the complexes A and B, respectively.

Zinc Porphyrin-Cored Dendrimers; Axial Coordination of Pyridine and Photoinduced Electron Transfer to Methyl Viologen

  • Park, Ji-Eun;Choi, Dae-Ock;Shin, Eun-Ju
    • Bulletin of the Korean Chemical Society
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    • v.32 no.12
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    • pp.4247-4252
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    • 2011
  • The porphyrin-incorporated arylether dendrimers ZnP-D1 and ZnP-D4 were investigated to discover the influence of dendritic environments for the axial ligation of pyridine and photoinduced electron transfer by methyl viologen. Absorption and fluorescence spectra of ZnP, ZnP-D1, and ZnP-D4 were measured in dichloromethane with the addition of pyridine or methyl viologen dichloride. Axial ligation of pyridine was confirmed by red-shifted absorption spectrum. The complex formation constants $K_f$ (Table 1) for axial coordination of pyridine on ZnP, ZnP-D1, and ZnP-D4 were estimated to be $4.4{\times}10^3\;M^{-1}$, $3.3{\times}10^3\;M^{-1}$, and $1.7{\times}10^3\;M^{-1}$, respectively. The photoinduced electron transfer to methyl viologen dichloride was confirmed by fluorescence quenching. Stern-Volmer constants Ksv for ZnP, ZnP-D1, and ZnP-D4 were calculated to be $2.6{\times}10^3$, $2.5{\times}10^3$, and $2.1{\times}10^3$, respectively. ZnP-D4 surrounded by 4 aryl ether dendrons shows the smallest $K_f$ and Ksv values, with comparison to ZnP and ZnP-D1.